JP2011192402A - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

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JP2011192402A
JP2011192402A JP2010054989A JP2010054989A JP2011192402A JP 2011192402 A JP2011192402 A JP 2011192402A JP 2010054989 A JP2010054989 A JP 2010054989A JP 2010054989 A JP2010054989 A JP 2010054989A JP 2011192402 A JP2011192402 A JP 2011192402A
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positive electrode
electrolyte secondary
secondary battery
lithium
active material
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Kazufumi Ando
和史 安藤
Koji Abe
浩司 安部
Kazuhiro Miyoshi
和弘 三好
Masahide Kondo
正英 近藤
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Sanyo Electric Co Ltd
Ube Corp
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Sanyo Electric Co Ltd
Ube Industries Ltd
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Priority to JP2010054989A priority Critical patent/JP2011192402A/en
Priority to CN2011100520977A priority patent/CN102195090A/en
Priority to EP11156591A priority patent/EP2367229A1/en
Priority to US13/042,543 priority patent/US20110223490A1/en
Priority to KR1020110021354A priority patent/KR20110102831A/en
Publication of JP2011192402A publication Critical patent/JP2011192402A/en
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
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    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0034—Fluorinated solvents
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    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
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    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery having a long cycle life even when charged at a positive electrode charging potential of 4.4 to 4.6 V based on lithium and having a high residual capacity after storage at high temperature in a charged state. <P>SOLUTION: A positive electrode active material of the nonaqueous electrolyte secondary battery includes a mixture of a lithium-cobalt composite oxide containing at least both zirconium and magnesium, and a lithium-manganese-nickel composite oxide containing at least both manganese and nickel. A nonaqueous electrolyte of the nonaqueous electrolyte secondary battery includes: fluoroethylene carbonate and dimethyl carbonate as a nonaqueous solvent; and further an additive represented by the following general formula (1), wherein R is methyl or hydrogen atom, m is 0 or 1, and n is 1 or 2. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、高充電電圧で充電し得る非水電解質二次電池に関する。更に詳しくは、本発明は、正極の充電電位をリチウム基準で４．４〜４．６Ｖとして充電しても、サイクル寿命が長く、しかも高温充電保存後の残存容量率が大きい非水電解質二次電池に関する。   The present invention relates to a nonaqueous electrolyte secondary battery that can be charged at a high charge voltage. More specifically, the present invention provides a non-aqueous electrolyte secondary that has a long cycle life and a large residual capacity ratio after high-temperature charge storage even when the charge potential of the positive electrode is charged to 4.4 to 4.6 V based on lithium. It relates to batteries.

今日の携帯電話機、携帯型パーソナルコンピューター、携帯型音楽プレイヤー等の携帯型電子機器の駆動電源として、さらには、ハイブリッド電気自動車（ＨＥＶ）や電気自動車（ＥＶ）用の電源として、高エネルギー密度を有し、高容量であるリチウムイオン二次電池に代表される非水電解質二次電池が広く利用されている。   It has high energy density as a drive power source for portable electronic devices such as today's mobile phones, portable personal computers and portable music players, and also as a power source for hybrid electric vehicles (HEV) and electric vehicles (EV). However, non-aqueous electrolyte secondary batteries represented by high-capacity lithium ion secondary batteries are widely used.

これらの非水電解質二次電池の正極活物質としては、リチウムイオンを可逆的に吸蔵・放出することが可能なＬｉＭＯ２（但し、ＭはＣｏ、Ｎｉ、Ｍｎの少なくとも１種である）で表されるリチウム遷移金属複合酸化物、すなわち、ＬｉＣｏＯ２、ＬｉＮｉＯ２、ＬｉＮｉｙＣｏ１−ｙＯ２（ｙ＝０．０１〜０．９９）、ＬｉＭｎＯ２、ＬｉＭｎ２Ｏ４、ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）、又はＬｉＦｅＰＯ４などが一種単独もしくは複数種を混合して用いられている。 The positive electrode active material of these nonaqueous electrolyte secondary batteries is represented by LiMO 2 (where M is at least one of Co, Ni, and Mn) capable of reversibly occluding and releasing lithium ions. Lithium transition metal composite oxides, that is, LiCoO 2 , LiNiO 2 , LiNi y Co 1-y O 2 (y = 0.01 to 0.99), LiMnO 2 , LiMn 2 O 4 , LiNi x Mn y Co z O 2 (x + y + z = 1), LiFePO 4 or the like is used singly or in combination.

このうち、特に各種電池特性が他のものに対して優れていることから、リチウムコバルト複合酸化物や異種金属元素添加リチウムコバルト複合酸化物が多く使用されている。しかしながら、コバルトは高価であると共に資源としての存在量が少ない。そのため、これらのリチウムコバルト複合酸化物や異種金属元素添加リチウムコバルト複合酸化物を非水電解質二次電池の正極活物質として使用し続けるには、非水電解質二次電池のさらなる高性能化が望まれている。   Among these, since various battery characteristics are particularly excellent with respect to others, lithium cobalt composite oxides and heterogeneous metal element-added lithium cobalt composite oxides are often used. However, cobalt is expensive and has a small abundance as a resource. Therefore, in order to continue using these lithium cobalt composite oxides and lithium cobalt composite oxides added with different metal elements as the positive electrode active material of the non-aqueous electrolyte secondary battery, further enhancement of the performance of the non-aqueous electrolyte secondary battery is desired. It is rare.

このようなリチウムコバルト複合酸化物を正極活物質として用いた非水電解質二次電池の高容量化の手段の一つとして、充電終止電圧をリチウム基準で４．４〜４．６Ｖ程度まで引き上げる方法が知られている。例えば、上述のＬｉＣｏＯ２などのリチウム含有遷移金属酸化物を正極活物質として用い、黒鉛等の炭素材料を負極活物質として用いた非水電解質二次電池においては、一般に充電電圧は４．１〜４．２Ｖ（正極電位はリチウム基準で４．２〜４．３Ｖ）となっている。このような充電条件では、正極は理論容量に対して５０〜６０％しか利用されていないことになる。したがって、非水電解質二次電池の充電電圧をより高くすることができれば、正極の容量を理論容量に対して７０％以上で利用することが可能となり、限られた体積内で効率的に容量アップを図ることができるようになる。 As one means for increasing the capacity of a non-aqueous electrolyte secondary battery using such a lithium cobalt composite oxide as a positive electrode active material, a method of raising the end-of-charge voltage to about 4.4 to 4.6 V based on lithium It has been known. For example, in a non-aqueous electrolyte secondary battery using a lithium-containing transition metal oxide such as LiCoO 2 described above as a positive electrode active material and a carbon material such as graphite as a negative electrode active material, the charging voltage is generally 4.1 to It is 4.2 V (the positive electrode potential is 4.2 to 4.3 V based on lithium). Under such charging conditions, the positive electrode is used only 50 to 60% of the theoretical capacity. Therefore, if the charging voltage of the non-aqueous electrolyte secondary battery can be increased, the capacity of the positive electrode can be used at 70% or more of the theoretical capacity, and the capacity can be efficiently increased within a limited volume. Can be planned.

また、非水電解質二次電池の高容量化のもう一つの手法として、電極材料の充填密度を高くする方法がある。近年の高容量型の非水電解質二次電池は、これらの充電電圧のアップと極板の充填密度アップの手法を組み合わせて作製されている。   Another method for increasing the capacity of the nonaqueous electrolyte secondary battery is to increase the packing density of the electrode material. High-capacity non-aqueous electrolyte secondary batteries in recent years are produced by combining these methods of increasing the charging voltage and increasing the packing density of the electrode plates.

このようにして作製される非水電解質二次電池は、高い充電電圧と充填密度が特徴であるため、正極活物質には高い耐酸化性が求められている。更に、非水電解液には高い耐酸化性に加えて、密度の高い極板中にも容易に浸透できる能力が要求されている。このような正極材料の耐酸化性、非水電解質の耐酸化性及び高浸透性は、どちらも高容量かつ高電圧の非水電解質二次電池には欠かせない要素である。   Since the nonaqueous electrolyte secondary battery produced in this way is characterized by a high charging voltage and a filling density, high positive electrode active material is required to have high oxidation resistance. Furthermore, in addition to high oxidation resistance, non-aqueous electrolytes are required to have the ability to easily penetrate into dense electrode plates. Such oxidation resistance of the positive electrode material, oxidation resistance of the nonaqueous electrolyte, and high permeability are all indispensable elements for a high capacity, high voltage nonaqueous electrolyte secondary battery.

正極活物質の耐酸化性を確保する手法としては、下記特許文献１に示されているように、リチウムコバルト複合酸化物にジルコニウム（Ｚｒ）とマグネシウム（Ｍｇ）を添加すると共に、リチウムマンガンニッケル複合酸化物を組み合わせて用いる手法がある。正極活物質としてこれらの材料を用いると、正極材料からの遷移金属イオン溶出にともなう劣化を抑制することができ、充電電圧を正極電位がリチウム基準で４．３Ｖを超える電圧としても、良好なサイクル特性と熱安定性を達成し得る非水電解質二次電池が得られている。   As a technique for ensuring the oxidation resistance of the positive electrode active material, as shown in Patent Document 1 below, zirconium (Zr) and magnesium (Mg) are added to a lithium cobalt composite oxide, and a lithium manganese nickel composite is added. There is a method using a combination of oxides. When these materials are used as the positive electrode active material, deterioration due to elution of transition metal ions from the positive electrode material can be suppressed, and a good cycle can be obtained even when the charging voltage is a voltage where the positive electrode potential exceeds 4.3 V on the basis of lithium. Non-aqueous electrolyte secondary batteries capable of achieving characteristics and thermal stability have been obtained.

上述のように、高充電電圧下における正極活物質の耐酸化性を確保する手法は既に知られている。しかしながら、正極活物質上での非水電解液の分解は、これらの正極材料を用いても抑制することはできない。そのため、非水電解質二次電池においては、高充電電圧下における耐酸化性を向上させた非水電解液と組み合わせないと、高充電電圧下における優れた電池性能は期待できない。   As described above, a method for ensuring the oxidation resistance of the positive electrode active material under a high charging voltage is already known. However, the decomposition of the nonaqueous electrolytic solution on the positive electrode active material cannot be suppressed even if these positive electrode materials are used. Therefore, in a non-aqueous electrolyte secondary battery, excellent battery performance under a high charging voltage cannot be expected unless combined with a non-aqueous electrolyte with improved oxidation resistance under a high charging voltage.

非水電解液の耐酸化性を向上させる手法としては、エチレンカーボネートの代わりにフルオロエチレンカーボネートを用いる方法が有効である。このフルオロエチレンカーボネートと前記の正極材料を組み合わせることで、優れた耐酸化性をもつ非水電解質二次電池が得られるが、これらの組み合わせだけでは十分なサイクル寿命を得ることが困難である。   As a method for improving the oxidation resistance of the nonaqueous electrolytic solution, a method using fluoroethylene carbonate instead of ethylene carbonate is effective. By combining this fluoroethylene carbonate and the above positive electrode material, a non-aqueous electrolyte secondary battery having excellent oxidation resistance can be obtained, but it is difficult to obtain a sufficient cycle life only by these combinations.

非水電解質二次電池のサイクル寿命特性を向上させる技術としては、非水電解液に鎖状カーボネートを添加する技術が広く知られている。非水電解質二次電池のサイクル寿命特性は、非水電解液の導電率が高く、かつ粘度が低いほど、向上する。これは、非水電解液中のリチウムイオンの移動が円滑になり、極板中への電解液の浸透が速くなるからである。特に、鎖状カーボネートのうち、ジメチルカーボネート（以下、「ＤＭＣ」という。）はこれらの条件を良好に満たしているため、非水電解液中に適量を添加することでサイクル寿命が大きく向上する。   As a technique for improving the cycle life characteristics of a non-aqueous electrolyte secondary battery, a technique for adding a chain carbonate to a non-aqueous electrolyte is widely known. The cycle life characteristics of the nonaqueous electrolyte secondary battery are improved as the conductivity of the nonaqueous electrolyte is higher and the viscosity is lower. This is because the movement of lithium ions in the non-aqueous electrolyte is smooth, and the penetration of the electrolyte into the electrode plate is accelerated. In particular, among the chain carbonates, dimethyl carbonate (hereinafter referred to as “DMC”) satisfies these conditions satisfactorily, so that the cycle life is greatly improved by adding an appropriate amount to the non-aqueous electrolyte.

その一方で、鎖状カーボネートは負極上で還元されやすく、高温環境下で充電状態で長期間保存すると、自己放電を起こす特徴がある。そのため、従来から、有機溶媒の還元分解を抑制するために、様々な化合物を非水電解液に添加して、負極活物質が有機溶媒と直接反応しないようにするため、不動態化層とも称される負極表面被膜（ＳＥＩ：Solid Electrolyte Interface．以下、「ＳＥＩ表面被膜」という。）を形成する技術が知られている。   On the other hand, the chain carbonate is easily reduced on the negative electrode, and is characterized by self-discharge when stored in a charged state for a long time in a high temperature environment. Therefore, conventionally, in order to suppress the reductive decomposition of the organic solvent, various compounds are added to the non-aqueous electrolyte so that the negative electrode active material does not directly react with the organic solvent. A technique of forming a negative electrode surface coating (SEI: Solid Electrolyte Interface. Hereinafter referred to as “SEI surface coating”) is known.

例えば、下記特許文献２及び３には、非水電解質二次電池の非水電解液の添加剤としてビニレンカーボネート（以下、「ＶＣ」という。）及びその誘導体から選択される少なくとも１種を添加したものを用い、最初の充電による負極へのリチウムの挿入前に、自ら負極表面で還元分解を起こすことにより負極活物質上にＳＥＩ表面被膜を形成させ、リチウムイオンの周囲の溶媒分子の挿入を阻止するバリアーとして機能させるようになした発明が開示されている。   For example, in Patent Documents 2 and 3 below, at least one selected from vinylene carbonate (hereinafter referred to as “VC”) and derivatives thereof is added as an additive for the non-aqueous electrolyte solution of the non-aqueous electrolyte secondary battery. Before the insertion of lithium into the negative electrode by the first charge, the SEI surface film is formed on the negative electrode active material by causing reductive decomposition on the negative electrode surface to prevent the insertion of solvent molecules around the lithium ion An invention designed to function as a barrier is disclosed.

このときのＶＣの必要量は、初期のＳＥＩ表面皮膜形成に必要な量（約１％前後）と長期にわたって皮膜を補修するのに必要な量（約０．５〜２％）の２つに分けて考えることができ、各種非水電解質二次電池の材料構成に合わせて、これら初期用＋補修用のト一タル量を添加するのが一般的な使い方であった。   The required amount of VC at this time is two, the amount necessary for initial SEI surface film formation (about 1%) and the amount necessary for repairing the film over a long period (about 0.5-2%). It can be considered separately, and it was a general usage to add these initial amount + total amount for repair according to the material composition of various nonaqueous electrolyte secondary batteries.

特開２００５−３１７４９９号公報JP 2005-317499 A 特開平 ８− ４５５４５号公報JP-A-8-45545 国際特許公開ＷＯ２００５／００８８２９International Patent Publication WO2005 / 008829

ところが、補修用のＶＣを添加しても非水電解質二次電池の正極の充電電位をリチウム基準で従来の４．３Ｖから４．４Ｖ以上に高くした場合には、高温充電保存特性は満足できるものではなかった。これは、正極電位を高電位としたために、補修用ＶＣが正極側で酸化され、ＶＣ自身が自己放電の原因となっていることによるものと考えられる。   However, even if VC for repair is added, if the charge potential of the positive electrode of the nonaqueous electrolyte secondary battery is increased from 4.3 V to 4.4 V or more based on lithium, the high temperature charge storage characteristics can be satisfied. It was not a thing. This is considered to be because the repairing VC is oxidized on the positive electrode side and the VC itself causes self-discharge because the positive electrode potential is set to a high potential.

この現象により、上述のような耐酸化性を確保できる正極活物質と、フルオロエチレンカーボネート及び鎖状カーボネートを組み合わせた非水電解液とを用い、正極の充電電位をリチウム基準で４．４Ｖ以上とした非水電解質二次電池では、サイクル特性と高温充電保存特性を両立させることが非常に困難であった。   Due to this phenomenon, a positive electrode active material that can ensure oxidation resistance as described above and a non-aqueous electrolyte combined with fluoroethylene carbonate and chain carbonate, and the positive electrode charging potential is 4.4 V or more based on lithium. In the nonaqueous electrolyte secondary battery, it was very difficult to achieve both cycle characteristics and high-temperature charge storage characteristics.

本発明は、上述のような従来技術の問題点を解決すべくなされたものであり、特にＶＣの代わりに他の有機添加剤を添加することによって、正極の充電電位をリチウム基準で４．４Ｖ以上とすることができ、しかも、高いサイクル寿命特性を保ったまま、高温充電保存時の自己放電を抑制することができる非水電解質二次電池を提供することを目的とする。   The present invention has been made to solve the above-mentioned problems of the prior art, and in particular, by adding another organic additive in place of VC, the charging potential of the positive electrode is 4.4 V with respect to lithium. An object of the present invention is to provide a non-aqueous electrolyte secondary battery that can suppress the self-discharge during high-temperature charge storage while maintaining high cycle life characteristics.

前記目的を達成するため、本発明の非水電解質二次電池は、
正極活物質を有する正極と、負極活物質を有する負極と、非水電解質と、セパレータとを備える非水電解質二次電池において、
前記正極活物質は、少なくともジルコニウム及びマグネシウムの両方を含有するリチウムコバルト複合酸化物と、少なくともマンガンとニッケルの両方を含有するリチウムマンガンニッケル複合酸化物との混合物からなり、
前記非水電解質は、非水溶媒としてフルオロエチレンカーボネート及びジメチルカーボネートを含み、更に、下記一般式（１）

Figure 2011192402
（ただし、Ｒはメチル基又は水素原子を表し、ｍは０又は１、ｎは１又は２を表す。）
で表される添加剤を含み、
前記正極の充電電位はリチウム基準で４．４〜４．６Ｖであることを特徴とする。 In order to achieve the above object, the non-aqueous electrolyte secondary battery of the present invention comprises:
In a nonaqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, a nonaqueous electrolyte, and a separator,
The positive electrode active material is composed of a mixture of a lithium cobalt composite oxide containing at least both zirconium and magnesium and a lithium manganese nickel composite oxide containing at least both manganese and nickel,
The non-aqueous electrolyte contains fluoroethylene carbonate and dimethyl carbonate as a non-aqueous solvent, and further includes the following general formula (1)
Figure 2011192402
 (However, R represents a methyl group or a hydrogen atom, m represents 0 or 1, and n represents 1 or 2.)
An additive represented by
The charging potential of the positive electrode is 4.4 to 4.6 V based on lithium.

本発明の非水電解質二次電池は、正極活物質として、少なくともジルコニウム及びマグネシウムの両方を含有するリチウムコバルト複合酸化物と、少なくともマンガンとニッケルの両方を含有するリチウムマンガンニッケル複合酸化物との混合物からなるものを用いている。この正極活物質は、正極の充電電位をリチウム基準で４．４Ｖ以上４．６Ｖ以下としても、耐酸化性が良好であるので、容量の大きな非水電解質二次電池が得られる。なお、リチウムコバルト複合酸化物中には、他にアルミニウム、チタン等の元素が含まれているとより好ましい。   The nonaqueous electrolyte secondary battery of the present invention is a mixture of a lithium cobalt composite oxide containing at least both zirconium and magnesium as a positive electrode active material and a lithium manganese nickel composite oxide containing at least both manganese and nickel. The thing which consists of is used. Since this positive electrode active material has good oxidation resistance even when the charge potential of the positive electrode is 4.4 V or more and 4.6 V or less on the basis of lithium, a non-aqueous electrolyte secondary battery having a large capacity can be obtained. In addition, it is more preferable that other elements such as aluminum and titanium are contained in the lithium cobalt composite oxide.

また、本発明の非水電解質二次電池においては、前記非水溶媒は、フルオロエチレンカーボネート及びジメチルカーボネートを含んでいることが必要である。   In the non-aqueous electrolyte secondary battery of the present invention, the non-aqueous solvent needs to contain fluoroethylene carbonate and dimethyl carbonate.

フルオロエチレンカーボネートは、環状カーボネートの一種であるが、一般的な環状カーボネートと比べて酸化分解及び還元分解され難い。フルオロエチレンカーボネートの含有量は、非水溶媒の総体積に対して１０〜４０体積％が好ましく、１５〜３５体積％が特に好ましい。フルオロエチレンカーボネートの含有量が少ないと高電位における耐酸化性が不十分となり、その含有量が多すぎると溶媒の粘度が高くなるため、極板中への液浸透性の低下に伴い、サイクル特性が低下する。   Fluoroethylene carbonate is a kind of cyclic carbonate, but is less susceptible to oxidative decomposition and reductive decomposition than general cyclic carbonate. 10-40 volume% is preferable with respect to the total volume of a non-aqueous solvent, and, as for content of fluoroethylene carbonate, 15-35 volume% is especially preferable. When the content of fluoroethylene carbonate is low, the oxidation resistance at high potential becomes insufficient, and when the content is too high, the viscosity of the solvent increases, and as a result, the liquid permeability into the electrode plate decreases. Decreases.

ジメチルカーボネートは、鎖状カーボネートの中でも最も粘度が低いため、溶媒全体の粘度を下げるのに好適である。ジメチルカーボネートを用いることで、極板中への液浸透性が向上するため、サイクル特性が向上する。ジメチルカーボネートの含有量は、非水溶媒の総体積に対して５〜５０体積％が好ましく、１０〜４０体積％がより好ましく、１５〜３５体積％が特に好ましい。ジメチルカーボネートの含有量が少ないと溶媒の粘度が高くなり、サイクル特性が低下する場合がある。その含有量が多すぎると、溶媒の耐酸化性が低下するため、サイクル特性、保存特性が低下する場合がある。   Since dimethyl carbonate has the lowest viscosity among chain carbonates, it is suitable for reducing the viscosity of the entire solvent. By using dimethyl carbonate, the liquid permeability into the electrode plate is improved, so that the cycle characteristics are improved. The content of dimethyl carbonate is preferably 5 to 50% by volume, more preferably 10 to 40% by volume, and particularly preferably 15 to 35% by volume with respect to the total volume of the nonaqueous solvent. If the content of dimethyl carbonate is small, the viscosity of the solvent increases, and the cycle characteristics may deteriorate. If the content is too large, the oxidation resistance of the solvent is lowered, so that the cycle characteristics and the storage characteristics may be lowered.

そして、本発明の非水電解質二次電池では、非水電解質中に上記一般式（１）で表される添加剤を含んでいる。
上記一般式（１）で表される化合物は、ＶＣの場合と同様に、ＳＥＩ表面被膜を形成する機能を備えていると共に、ＶＣよりも高い耐酸化性を備えている。そのため、本発明の非水電解質二次電池によれば、負極活物質と有機溶媒とが直接反応し難くなるので、有機溶媒の分解を抑制することができるようになる。 And in the nonaqueous electrolyte secondary battery of this invention, the additive represented by the said General formula (1) is included in the nonaqueous electrolyte.
The compound represented by the general formula (1) has a function of forming an SEI surface film as well as VC, and has higher oxidation resistance than VC. Therefore, according to the nonaqueous electrolyte secondary battery of the present invention, it becomes difficult for the negative electrode active material and the organic solvent to react directly, so that the decomposition of the organic solvent can be suppressed.

加えて、高温充電保存時にＳＥＩ被膜の欠損が生じても、この欠損は上記一般式（１）で表される化合物によって補修される。そのため、本発明の非水電解質二次電池によれば、正極の充電電位をリチウム基準で４．４Ｖ以上としても、高いサイクル寿命特性を保ったまま、高温充電保存時の自己放電を抑制することができる非水電解質二次電池が得られる。なお、正極の充電電位がリチウム基準で４．６Ｖを超えると、正極活物質が劣化するため、好ましくない。   In addition, even if the SEI film is deficient during storage at high temperature, this deficiency is repaired by the compound represented by the general formula (1). Therefore, according to the non-aqueous electrolyte secondary battery of the present invention, even if the charge potential of the positive electrode is 4.4 V or more on the basis of lithium, self-discharge during high-temperature charge storage is maintained while maintaining high cycle life characteristics. A non-aqueous electrolyte secondary battery that can be obtained is obtained. Note that when the charge potential of the positive electrode exceeds 4.6 V on the basis of lithium, the positive electrode active material deteriorates, which is not preferable.

前記一般式（１）で表される具体的な化合物として、２−（メタンスルホニルオキシ）プロピオン酸２−プロピニル、２−（メタンスルホニルオキシ）プロピオン酸３−ブチニル、メタンスルホニルオキシ酢酸２−プロピニル、メタンスルホニルオキシ酢酸３−ブチニル、メタンスルホン酸２−プロピニル及びメタンスルホン酸３−ブチニルが挙げられるが、好ましくは２−（メタンスルホニルオキシ）プロピオン酸２−プロピニル、メタンスルホニルオキシ酢酸２−プロピニル、又はメタンスルホン酸２−プロピニルが好ましい。さらに好ましくは、２−（メタンスルホニルオキシ）プロピオン酸２−プロピニル、又はメタンスルホン酸２−プロピニルである。   Specific compounds represented by the general formula (1) include 2-propynyl 2- (methanesulfonyloxy) propionate, 3-butynyl 2- (methanesulfonyloxy) propionate, 2-propynyl methanesulfonyloxyacetate, Examples include 3-butynyl methanesulfonyloxyacetate, 2-propynyl methanesulfonate and 3-butynyl methanesulfonate, preferably 2-propynyl 2- (methanesulfonyloxy) propionate, 2-propynyl methanesulfonyloxyacetate, or 2-propynyl methanesulfonate is preferred. More preferred is 2-propynyl 2- (methanesulfonyloxy) propionate or 2-propynyl methanesulfonate.

前記一般式（１）で表される化合物は、２つ以上組み合わせて使用することもでき、特に２−（メタンスルホニルオキシ）プロピオン酸２−プロピニルとメタンスルホン酸２−プロピニルを組み合わせて使用することが好ましい。
添加剤の含有量は、非水電解質の総質量に対して０．２〜２質量％が好ましい。 Two or more compounds represented by the general formula (1) may be used in combination, and in particular, 2- (methanesulfonyloxy) propionic acid 2-propynyl and methanesulfonic acid 2-propynyl may be used in combination. Is preferred.
The content of the additive is preferably 0.2 to 2% by mass with respect to the total mass of the nonaqueous electrolyte.

なお、本発明の非水電解質二次電池の非水電解質で用いることができる電解質塩としては、従来の非水電解質二次電池において電解質として一般に使用されているものを用いることができ、例えば、ＬｉＢＦ４、ＬｉＰＦ６、ＬｉＣＦ３ＳＯ３、ＬｉＣ４Ｆ９ＳＯ３、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＮ（Ｃ２Ｆ５ＳＯ２）２、ＬｉＡｓＦ６、ジフルオロ（オキサラト）ホウ酸リチウムから選択される少なくとも１種を用いることができる。これら電解質は、前記非水溶媒に対して０．５〜２ｍｏｌ／Ｌの濃度で使用することが好ましい。 In addition, as the electrolyte salt that can be used in the nonaqueous electrolyte of the nonaqueous electrolyte secondary battery of the present invention, those generally used as an electrolyte in conventional nonaqueous electrolyte secondary batteries can be used, for example, Selected from LiBF 4 , LiPF 6 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiAsF 6 , lithium difluoro (oxalato) borate At least one of the above can be used. These electrolytes are preferably used at a concentration of 0.5 to 2 mol / L with respect to the non-aqueous solvent.

また、本発明で用いる負極としては、リチウム金属、リチウム合金、黒鉛等の炭素材料、珪素材料、リチウム複合酸化物などのリチウムを吸蔵・放出することができる材料が挙げられる。   Examples of the negative electrode used in the present invention include materials capable of inserting and extracting lithium, such as carbon materials such as lithium metal, lithium alloy, and graphite, silicon materials, and lithium composite oxides.

また、本発明の非水電解質二次電池においては、前記非水電解質は、前記添加剤として更にＶＣを含んでいることが好ましい。   In the nonaqueous electrolyte secondary battery of the present invention, it is preferable that the nonaqueous electrolyte further contains VC as the additive.

ＶＣは、上記一般式（１）で表される化合物よりもＳＥＩ表面被膜を形成し易い。そのため、非水電解質二次電池の非水電解質中に上記一般式（１）で表される化合物とＶＣとが共存していると、最初にＶＣによるＳＥＩ表面被膜が形成される。そして、ＶＣが全て消費された後にＳＥＩ被膜の欠損が生じても、この欠損は上記一般式（１）で表される化合物によって補修される。   VC forms a SEI surface film more easily than the compound represented by the general formula (1). Therefore, when the compound represented by the general formula (1) and VC coexist in the nonaqueous electrolyte of the nonaqueous electrolyte secondary battery, an SEI surface film is first formed by VC. And even if the defect of the SEI film occurs after all the VC is consumed, the defect is repaired by the compound represented by the general formula (1).

しかも、ＶＣが全て消費された後は、高温充電保存時のＶＣと正極活物質との間の反応に由来する自己放電は起こらず、しかも、上記一般式（１）で表される化合物が消費されずに残っているので、長期間に亘ってＳＥＩ表面皮膜が補修され、高温充電保存時の非水電解質と負極活物質との反応に由来する自己放電も抑制され、サイクル寿命が更に向上する。なお、ＶＣの添加量は、初期のＳＥＩ表面被膜が形成される量程度（非水電解質総量の約１質量％程度）とすることが好ましいが、それよりも僅かに多くても特に問題は生じない。したがって、ＶＣの添加量は、好ましくは０．１〜１．５質量％、更に好ましくは０．５〜１質量％である。   Moreover, after all the VC is consumed, no self-discharge resulting from the reaction between the VC and the positive electrode active material during storage at high temperature charge occurs, and the compound represented by the general formula (1) is consumed. As a result, the SEI surface film is repaired over a long period of time, self-discharge resulting from the reaction between the nonaqueous electrolyte and the negative electrode active material during high-temperature charge storage is suppressed, and the cycle life is further improved. . The amount of VC added is preferably about the amount that the initial SEI surface film is formed (about 1% by mass of the total amount of the non-aqueous electrolyte), but even if it is slightly larger than that, there is a particular problem. Absent. Therefore, the amount of VC added is preferably 0.1 to 1.5% by mass, more preferably 0.5 to 1% by mass.

また、本発明の非水電解質二次電池においては、前記一般式（１）で表される化合物が、下記化学構造式（２）又は（３）で表される化合物であることが好ましい。

Figure 2011192402
Figure 2011192402
 In the nonaqueous electrolyte secondary battery of the present invention, the compound represented by the general formula (1) is preferably a compound represented by the following chemical structural formula (2) or (3).
Figure 2011192402
Figure 2011192402

上記化学構造式（２）で表される化合物はＰＭＰ（２−（メタンスルホニルオキシ）プロピオン酸２−プロピニル）として知られているものであり、上記化学構造式（３）で表される化合物はＭＳＰ（メタンスルホン酸２−プロピニル）として知られている化合物である。このようなＰＭＰ及びＭＳＰを使用すると、上記効果が顕著に現れる。   The compound represented by the chemical structural formula (2) is known as PMP (2- (propynyl 2- (methanesulfonyloxy) propionate)), and the compound represented by the chemical structural formula (3) is It is a compound known as MSP (2-propynyl methanesulfonate). When such PMP and MSP are used, the above-mentioned effect is remarkably exhibited.

また、本発明の非水電解質二次電池においては、前記リチウムマンガンニッケル複合酸化物は、ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）で表される化合物であり、前記正極活物質の全質量を１００質量部としたとき、前記ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）混合量を５〜２５質量部とすることができる。 In the nonaqueous electrolyte secondary battery of the present invention, the lithium-manganese-nickel composite oxide is a compound represented by LiNi x Mn y Co z O 2 (x + y + z = 1), the total of the positive active material When the mass is 100 parts by mass, the amount of LiNi x Mn y Co z O 2 (x + y + z = 1) mixed can be 5 to 25 parts by mass.

正極活物質中のリチウムマンガンニッケル複合酸化物は、ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）で表される化合物であり、前記正極活物質の全質量を１００質量部としたとき、前記ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）混合量を５〜２５質量部とすると、特に上記効果が良好に現れる。その混合量が５質量部未満であると、高電位での正極活物質の熱的安定性が不十分であり、２５質量部を超えると電池容量、サイクル特性が不十分となるため、本発明の効果を十分に得ることができない。 The lithium manganese nickel composite oxide in the positive electrode active material is a compound represented by LiNi x Mn y Co z O 2 (x + y + z = 1), and when the total mass of the positive electrode active material is 100 parts by mass, When the mixing amount of LiNi x Mn y Co z O 2 (x + y + z = 1) is set to 5 to 25 parts by mass, the above-described effect appears particularly well. If the mixing amount is less than 5 parts by mass, the thermal stability of the positive electrode active material at a high potential is insufficient, and if it exceeds 25 parts by mass, the battery capacity and cycle characteristics become insufficient. The effect of can not be fully obtained.

また、本発明の非水電解質二次電池においては、前記非水溶媒は、鎖状カーボネートとして非対称カーボネートを含むことが好ましく、特にメチルエチルカーボネートを含むことが好ましい。   In the nonaqueous electrolyte secondary battery of the present invention, the nonaqueous solvent preferably contains an asymmetric carbonate as a chain carbonate, and particularly preferably contains methylethyl carbonate.

メチルエチルカーボネートは、ジメチルカーボネートと比較して耐酸化性に優れるため、ジメチルカーボネートと併用して使用することが好ましい。メチルエチルカーボネートの含有量は、非水溶媒中に１０〜７０体積％であることが好ましく、２０〜５０体積％であることがより好ましい。   Since methyl ethyl carbonate is superior in oxidation resistance compared to dimethyl carbonate, it is preferably used in combination with dimethyl carbonate. The content of methyl ethyl carbonate is preferably 10 to 70% by volume in the non-aqueous solvent, and more preferably 20 to 50% by volume.

以下、本発明を実施するための形態を実施例及び比較例を用いて詳細に説明する。但し、以下に示す実施例は、本発明の技術思想を具体化するための非水電解質二次電池の一例を示すものであって、本発明をこの実施例に限定することを意図するものではなく、本発明は特許請求の範囲に示した技術思想を逸脱することなく種々の変更を行ったものにも均しく適用し得るものである。   Hereinafter, the form for implementing this invention is demonstrated in detail using an Example and a comparative example. However, the following examples show one example of a nonaqueous electrolyte secondary battery for embodying the technical idea of the present invention, and are not intended to limit the present invention to this example. The present invention can be equally applied to various modifications without departing from the technical idea shown in the claims.

最初に、各種実施例及び比較例で共通する非水電解質二次電池の具体的製造方法について説明する。
［正極極板の作製］
実施例１〜４及び比較例１〜３で使用する正極活物質は、層状ニッケルマンガンコバルト酸リチウム（ＬｉＮｉ１／３Ｍｎ１／３Ｃｏ１／３Ｏ２）とマグネシウム、アルミニウム、ジルコニウム含有コバルト酸リチウム（ＬｉＣｏ０．９７３Ｍｇ０．００５Ａｌ０．０２Ｚｒ０．００２Ｏ２）を質量比で１:９の割合で混合したものを用いた（以下、「ハイブリッド正極活物質」という。）。このハイブリッド正極活物質を、導電助剤としてのカーボンブラック（例えば、「ケッチェンブラック」（商品名））と、結着剤としてのフッ素樹脂とを質量比で９４:３:３の割合で混合し、これをＮ−メチル−２−ピロリドン（ＮＭＰ）に溶解してぺーストとした。 First, a specific method for manufacturing a nonaqueous electrolyte secondary battery common to various examples and comparative examples will be described.
[Preparation of positive electrode plate]
The positive electrode active materials used in Examples 1 to 4 and Comparative Examples 1 to 3 are layered lithium manganese manganese cobaltate (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ), magnesium, aluminum, and zirconium-containing cobalt acid. Lithium (LiCo 0.973 Mg 0.005 Al 0.02 Zr 0.002 O 2 ) mixed at a mass ratio of 1: 9 was used (hereinafter referred to as “hybrid positive electrode active material”). This hybrid positive electrode active material is mixed with carbon black (for example, “Ketjen Black” (trade name)) as a conductive additive and fluororesin as a binder in a mass ratio of 94: 3: 3. This was dissolved in N-methyl-2-pyrrolidone (NMP) to obtain a paste.

このぺーストをドクターブレード法により厚み１５μｍのアルミニウム箔の両面に均一に塗布した。次に、加熱した乾燥機中で１００〜１５０℃の温度で真空熱処理してＮＭＰを除去後、厚みが０．１３ｍｍになるようにロールプレス機により圧延して正極極板を作製した。   This paste was uniformly applied to both surfaces of an aluminum foil having a thickness of 15 μm by a doctor blade method. Next, the NMP was removed by vacuum heat treatment at a temperature of 100 to 150 ° C. in a heated drier, and then rolled with a roll press so as to have a thickness of 0.13 mm to produce a positive electrode plate.

また、比較例４及び６で使用する正極活物質はＬｉＣｏＯ２を単独で用い、比較例５及び７で用いる正極活物質はマグネシウム、アルミニウム、ジルコニウム含有コバルト酸リチウム（ＬｉＣｏ０．９７３Ｍｇ０．００５Ａｌ０．０２Ｚｒ０．００２Ｏ２）を単独で用いた他は、上記と同様にして正極活物質を作製した。 The positive electrode active material used in Comparative Examples 4 and 6 is LiCoO 2 alone, and the positive electrode active material used in Comparative Examples 5 and 7 is magnesium, aluminum, zirconium-containing lithium cobaltate (LiCo 0.973 Mg 0.005 A positive electrode active material was prepared in the same manner as described above except that Al 0.02 Zr 0.002 O 2 ) was used alone.

［負極極板の作製］
実施例１〜４及び比較例１から７に共通する負極極板は以下のようにして作製した。まず、黒鉛からなる負極活物質と、結着剤としてのスチレンブタジエンゴム（ＳＢＲ）と、粘度調整剤としての力ルボキシメチルセルロース（ＣＭＣ）を質量比で９６:２:２の割合で混合したものを水に溶解してぺーストとした。このぺーストをドクターブレード法により厚み１０μｍの銅箔の両面に均一に塗布した。その後、加熱した乾燥機中で１００〜１５０℃の温度で加熱処理して水分を除去した後、厚みが０．１２ｍｍになるようロールプレス機により圧延して負極極板を作製した。なお、負極極板の活物質塗布量は、対向する正極極板の単位面積あたりの初期充電容量に対して、単位面積あたりの負極初期充電容量が１００％以上となるよう適宜塗布質量を変更し、かつ負極活物質の充填密度が同じになるよう厚みを適宜調整して負極極板の作製を行った。 [Production of negative electrode plate]
Negative electrode plates common to Examples 1 to 4 and Comparative Examples 1 to 7 were produced as follows. First, a negative electrode active material made of graphite, styrene butadiene rubber (SBR) as a binder, and ruboxymethyl cellulose (CMC) as a viscosity modifier mixed at a mass ratio of 96: 2: 2. Was dissolved in water to make a paste. This paste was uniformly applied to both surfaces of a 10 μm thick copper foil by a doctor blade method. Then, after heat-processing in the heated dryer at the temperature of 100-150 degreeC and removing a water | moisture content, it rolled with the roll press machine so that thickness might be set to 0.12 mm, and produced the negative electrode plate. The amount of active material applied to the negative electrode plate is appropriately changed so that the negative electrode initial charge capacity per unit area is 100% or more with respect to the initial charge capacity per unit area of the opposite positive electrode plate. In addition, a negative electrode plate was prepared by appropriately adjusting the thickness so that the packing density of the negative electrode active material was the same.

［非水電解液の調整］
非水電解液は、フルオロエチレンカーボネート（ＦＥＣ）と、メチルエチルカーボネート（ＭＥＣ）、ジメチルカーボネート（ＤＭＣ）を適宜組合せ、更に、必要に応じてＶＣ、ＰＭＰ及びＭＳＰを適宜添加して作製した。具体的な組成比は、以下に示す表１及び表２に纏めて示した。なお、電解質塩としては、全てについてＬｉＰＦ６を１．０ｍｏｌ／Ｌとなるように添加して用いた。 [Adjustment of non-aqueous electrolyte]
The non-aqueous electrolyte was prepared by appropriately combining fluoroethylene carbonate (FEC), methyl ethyl carbonate (MEC), and dimethyl carbonate (DMC), and further adding VC, PMP, and MSP as necessary. Specific composition ratios are summarized in Tables 1 and 2 below. As the electrolyte salt, it is used by adding LiPF 6 for all so that 1.0 mol / L.

［非水電解質二次電池の作製］
上述のようにして作製された正極極板、負極極板及び非水電解液を用いて、実施例１〜４及び比較例１〜７に係る円筒形の非水電解質二次電池（容量２７００ｍＡｈ、高さ６５ｍｍ、直径１８ｍｍ）を作製した。なお、セパレータにはポリプロピレン製微多孔膜を用いた。 [Production of non-aqueous electrolyte secondary battery]
Using the positive electrode plate, the negative electrode plate and the non-aqueous electrolyte prepared as described above, cylindrical non-aqueous electrolyte secondary batteries (capacity 2700 mAh, according to Examples 1 to 4 and Comparative Examples 1 to 7, respectively) 65 mm in height and 18 mm in diameter) were produced. A polypropylene microporous membrane was used as the separator.

［高温充電保存特性］
高温充電保存特性は以下のとおりにして測定した。各電池を２５℃において、１Ｉｔ＝２７００ｍＡの定電流で充電し、電池電圧が４．３Ｖ（正極電位はリチウム基準で４．４Ｖ）に達した後は４．３Ｖの定電圧で充電電流が（１／５０）Ｉｔ＝５４ｍＡとなるまで充電し、満充電状態とした。その後、１Ｉｔ＝２７００ｍＡの定電流で電池電圧が３．０Ｖまで放電し、この放電時に流れた電荷量を測定して保存前容量として求めた。 [High-temperature charge storage characteristics]
The high-temperature charge storage characteristics were measured as follows. Each battery was charged at 25 ° C. with a constant current of 1 It = 2700 mA, and after the battery voltage reached 4.3 V (the positive electrode potential was 4.4 V with respect to lithium), the charging current was 4.3 V at a constant voltage ( 1/50) Charging was performed until It = 54 mA, and the battery was fully charged. Thereafter, the battery voltage was discharged to 3.0 V at a constant current of 1 It = 2700 mA, and the amount of charge that flowed at the time of discharge was measured to obtain the capacity before storage.

その後、１Ｉｔ＝２７００ｍＡの定電流で充電し、電池電圧が４．３Ｖ（正極電位はリチウム基準で４．４Ｖ）に達した後は４．３Ｖの定電圧で充電電流が（１／５０）Ｉｔ＝５４ｍＡとなるまで充電し、充電し、満充電状態とした後、６０℃に維持された恒温槽中に２０日間保存した。その後、各電池を２５℃になるまで冷却し、２５℃において１Ｉｔ＝２７００ｍＡの定電流で電池電圧が３．０Ｖまで放電した。この放電時に流れた電荷量を測定して保存後容量とし、以下の計算式により、高温充電保存特性として容量残存率（％）を求めた。結果をまとめて表１及び表２に示した。
容量残存率（％）＝（保存後容量／保存前容量）×１００ After that, the battery is charged with a constant current of 1 It = 2700 mA, and after the battery voltage reaches 4.3 V (the positive electrode potential is 4.4 V with respect to lithium), the charging current is (1/50) It with a constant voltage of 4.3 V. The battery was charged until it reached 54 mA, charged, and fully charged, and then stored in a thermostat maintained at 60 ° C. for 20 days. Thereafter, each battery was cooled to 25 ° C., and at 25 ° C., the battery voltage was discharged to 3.0 V with a constant current of 1 It = 2700 mA. The amount of charge that flowed during this discharge was measured to determine the capacity after storage, and the capacity remaining rate (%) was determined as the high-temperature charge storage characteristic by the following formula. The results are summarized in Tables 1 and 2.
Capacity remaining rate (%) = (capacity after storage / capacity before storage) × 100

［サイクル特性］
サイクル特性は、各電池を２５℃において１Ｉｔ＝２７００ｍＡの定電流で充電し、電池電圧が４．３Ｖ（正極電位はリチウム基準で４．４Ｖ）に達した後は４．３Ｖの定電圧で充電電流が（１／５０）Ｉｔ＝５４ｍＡとなるまで充電し、満充電状態とした。その後、１Ｉｔ＝２７００ｍＡの定電流で電池電圧が３．０Ｖまで放電して放電容量を測定するサイクルを３００サイクル繰り返して評価した。以下の計算式により、サイクル特性として容量維持率（％）を求め、結果をまとめて表１及び表２に示した。
容量維持率（％）＝（３００サイクル目の容量／１サイクル目の容量） [Cycle characteristics]
The cycle characteristics are as follows: Each battery is charged at a constant current of 1 It = 2700 mA at 25 ° C., and charged at a constant voltage of 4.3 V after the battery voltage reaches 4.3 V (the positive electrode potential is 4.4 V based on lithium). The battery was charged until the current reached (1/50) It = 54 mA to obtain a fully charged state. Thereafter, a cycle in which the battery voltage was discharged to 3.0 V at a constant current of 1 It = 2700 mA and the discharge capacity was measured was evaluated by repeating 300 cycles. The capacity retention rate (%) was obtained as the cycle characteristics by the following calculation formula, and the results are summarized in Tables 1 and 2.
Capacity maintenance ratio (%) = (capacity at 300th cycle / capacity at the first cycle)

Figure 2011192402
Figure 2011192402

表１に示した結果から、以下のことが分かる。すなわち、比較例１の電池では、ハイブリッド正極及びＦＥＣの組み合わせにより、正極の耐酸化性が確保された電池となっているが、充分なサイクル特性が得られていない。このことは、比較例１の電池では、非水溶媒中にＤＭＣが添加されていないため、非水溶媒の粘度が高くなり、非水電解液の極板への浸透が遅く、サイクル特性が低下したものと認められる。   From the results shown in Table 1, the following can be understood. That is, the battery of Comparative Example 1 is a battery in which the oxidation resistance of the positive electrode is ensured by the combination of the hybrid positive electrode and the FEC, but sufficient cycle characteristics are not obtained. This is because in the battery of Comparative Example 1, since DMC is not added to the non-aqueous solvent, the viscosity of the non-aqueous solvent is increased, the penetration of the non-aqueous electrolyte into the electrode plate is slow, and the cycle characteristics are degraded. It is recognized that

また、比較例２及び３の電池では、比較例１の非水溶媒中に対してＤＭＣを添加した結果、サイクル特性が向上しているが、高温充電保存特性が悪化している。このことは、非水溶媒中にＤＭＣが添加されたことにより、非水溶媒の粘度が低くなり、サイクル特性が向上したものと認められる。しかしながら、ＶＣ添加量が１質量％である比較例１及び２の電池では、ＶＣ添加量が少ないためにＶＣのほとんどは初期のＳＥＩ表面被膜の形成に使用され、高温充電保存時においては補修用のＶＣがほとんど残っていないはずである。しかしながら、非水溶媒中にＤＭＣが添加されている比較例２の電池は、非水溶媒中にＤＭＣが添加されていない比較例１の電池よりも高温充電保存特性が悪化している。このことは、比較例２の電池は、ＤＭＣと負極の副反応が起こったことにより、高温充電保存特性が低下したものと認められる。   Further, in the batteries of Comparative Examples 2 and 3, as a result of adding DMC to the non-aqueous solvent of Comparative Example 1, the cycle characteristics are improved, but the high-temperature charge storage characteristics are deteriorated. This is considered that the addition of DMC to the non-aqueous solvent lowered the viscosity of the non-aqueous solvent and improved the cycle characteristics. However, in the batteries of Comparative Examples 1 and 2 in which the VC addition amount is 1 mass%, since the VC addition amount is small, most of the VC is used for forming the initial SEI surface coating, and for repairing during high-temperature charge storage. There should be almost no VC left. However, the battery of Comparative Example 2 in which DMC is added in the non-aqueous solvent has deteriorated high-temperature charge storage characteristics as compared with the battery of Comparative Example 1 in which DMC is not added in the non-aqueous solvent. This indicates that the battery of Comparative Example 2 was deteriorated in high-temperature charge storage characteristics due to the side reaction between DMC and the negative electrode.

また、ＶＣ添加量が２質量％である比較例３の電池では、高温充電保存特性は、ＶＣの添加量が少ない比較例２の電池よりも良好であるが、ＤＭＣが添加されていない比較例１のものよりも劣っている。このことは、比較例３の電池では、ＶＣ添加量が多いため、高温充電保存時においてもＶＣが残っているが、このＶＣがＳＥＩ表面被膜の補修に使用されずに正極の表面で正極活物質との間で副反応を起こしたことにより、高温充電保存特性が低下したものと認められる。   Further, in the battery of Comparative Example 3 in which the VC addition amount is 2 mass%, the high-temperature charge storage characteristics are better than the battery of Comparative Example 2 in which the VC addition amount is small, but the Comparative Example in which DMC is not added. Inferior to one. This is because, in the battery of Comparative Example 3, since the amount of VC added is large, VC remains even during storage at high temperature charge. It is recognized that the high-temperature charge storage characteristics deteriorated due to a side reaction with the substance.

また、比較例４及び５では、非水溶媒中にＤＭＣ、ＶＣ及びＰＭＰが実施例１の場合と同量添加されているが、正極活物質として用いたＬｉＣｏＯ２（比較例４）及びＬｉＣｏ０．９７３Ｍｇ０．００５Ａｌ０．０２Ｚｒ０．００２Ｏ２（比較例５）の耐酸化性がハイブリッド正極活物質よりも劣るため、高温充電保存特性が低下したものと認められる。 In Comparative Examples 4 and 5, DMC, VC and PMP were added in the same amount as in Example 1 in the nonaqueous solvent, but LiCoO 2 (Comparative Example 4) and LiCo 0 used as the positive electrode active material. Since the oxidation resistance of .973 Mg 0.005 Al 0.02 Zr 0.002 O 2 (Comparative Example 5) is inferior to that of the hybrid positive electrode active material, it is recognized that the high-temperature charge storage characteristics were deteriorated.

それに対し、実施例１の電池では、非水溶媒中に初期のＳＥＩ表面皮膜形成用ＶＣ（１質量％）と長期のＳＥＩ表面皮膜補修用ＰＭＰ（１質量％）を添加したため、サイクル特性、高温充電保存特性ともに向上している。実施例１の測定結果と比較例２の測定結果を対比すると、実施例１の電池では、非水溶媒中にＰＭＰを添加することによって、ＳＥＩ表面皮膜の補修がなされていることがわかる。また、実施例１の測定結果と比較例３の測定結果を対比すると、ＰＭＰのＳＥＩ表面皮膜の補修効果は、高電圧高温充電保存環境においてはＶＣよりも優れていることが分かる。   On the other hand, in the battery of Example 1, the initial SEI surface film forming VC (1% by mass) and the long-term SEI surface film repairing PMP (1% by mass) were added to the non-aqueous solvent. Both charging and storage characteristics are improved. When the measurement result of Example 1 is compared with the measurement result of Comparative Example 2, it can be seen that in the battery of Example 1, the SEI surface film was repaired by adding PMP to the non-aqueous solvent. Moreover, when the measurement result of Example 1 and the measurement result of the comparative example 3 are contrasted, it turns out that the repair effect of the SEI surface film of PMP is superior to VC in a high voltage high temperature charge storage environment.

また、実施例２の電池では、ＳＥＩ表面皮膜形成用添加剤として、ＶＣを使用することなく、ＰＭＰのみとしたものであるが、実質的に実施例１の電池と同様の効果が得られている。このことは、ＰＭＰは、長期のＳＥＩ表面皮膜の補修効果だけでなく、初期のＳＥＩ表面皮膜形成用としての効果もＶＣと同程度に有していることがわかる。   Further, in the battery of Example 2, only SMP was used as the additive for forming the SEI surface film without using VC, but the same effect as the battery of Example 1 was obtained substantially. Yes. This indicates that PMP has not only the effect of repairing the SEI surface film for a long time but also the effect for forming the initial SEI surface film to the same extent as VC.

Figure 2011192402
Figure 2011192402

表２に示した結果から、以下のことが分かる。すなわち、実施例３及び４では、実施例１及び２に対して、ＰＭＰの代わりにＭＳＰを添加した結果、実施例１及び２と同様にそれぞれ保存特性が向上して、サイクル特性と高温保存特性の両立がなされている。ＭＳＰとＰＭＰは、保護皮膜の形成及び補修について同等の効果を有しており、両者に共通の構造をもつ化合物であれば、高充電電圧用の非水電解質二次電池において、同様のサイクル特性向上効果と高温充電保存特性の向上効果を有していることが示唆される。   From the results shown in Table 2, the following can be understood. That is, in Examples 3 and 4, as a result of adding MSP instead of PMP to Examples 1 and 2, the storage characteristics were improved similarly to Examples 1 and 2, respectively, and cycle characteristics and high-temperature storage characteristics were improved. The balance is made. MSP and PMP have the same effect on the formation and repair of the protective film, and the same cycle characteristics can be obtained in a non-aqueous electrolyte secondary battery for high charge voltage as long as the compound has a structure common to both. It is suggested that it has an improvement effect and an improvement effect of high temperature charge storage characteristics.

比較例６及び７ではＭＳＰが添加されているが、比較例４及び５の電池の場合と同じく、正極活物質がハイブリッド正極活物質ではないため、正極活物質中のＭｇ，Ａｌ，Ｚｒの異種元素の存在・不存在に関わらず、高温充電保存特性が不充分なものとなっていることがわかる。このことは、正極活物質の耐酸化性がハイブリッド正極より劣るためと思われる。   Although MSP is added in Comparative Examples 6 and 7, as in the case of the batteries of Comparative Examples 4 and 5, since the positive electrode active material is not a hybrid positive electrode active material, different types of Mg, Al, and Zr in the positive electrode active material. It can be seen that the high-temperature charge storage characteristics are insufficient regardless of the presence or absence of elements. This seems to be because the oxidation resistance of the positive electrode active material is inferior to that of the hybrid positive electrode.

したがって、実施例１の電池と比較例４及び５の電池の比較、及び、実施例３の電池と比較例６及び７の電池との比較により、ＭＳＰないしＰＭＰ添加の効果は、正極活物質としてハイブリッド正極活物質を用い、正極の充電電位をリチウム基準で４．４〜４．６Ｖとした場合に、有用であることがわかる。   Therefore, by comparing the battery of Example 1 with the batteries of Comparative Examples 4 and 5, and comparing the battery of Example 3 with the batteries of Comparative Examples 6 and 7, the effect of adding MSP or PMP is It turns out that it is useful when a hybrid positive electrode active material is used and the charge potential of the positive electrode is 4.4 to 4.6 V with respect to lithium.

Claims (5)

正極活物質を有する正極と、負極活物質を有する負極と、非水電解質と、セパレータとを備える非水電解質二次電池において、
前記正極活物質は、少なくともジルコニウム及びマグネシウムの両方を含有するリチウムコバルト複合酸化物と、少なくともマンガンとニッケルの両方を含有するリチウムマンガンニッケル複合酸化物との混合物からなり、
前記非水電解質は、非水溶媒としてフルオロエチレンカーボネート及びジメチルカーボネートを含み、更に、下記一般式（１）
Figure 2011192402
 （ただし、Ｒはメチル基又は水素原子を表し、ｍは０又は１、ｎは１又は２を表す。）
で表される添加剤を含み、
前記正極の充電電位はリチウム基準で４．４〜４．６Ｖであることを特徴とする非水電解質二次電池。 In a nonaqueous electrolyte secondary battery comprising a positive electrode having a positive electrode active material, a negative electrode having a negative electrode active material, a nonaqueous electrolyte, and a separator,
The positive electrode active material is composed of a mixture of a lithium cobalt composite oxide containing at least both zirconium and magnesium and a lithium manganese nickel composite oxide containing at least both manganese and nickel,
The non-aqueous electrolyte contains fluoroethylene carbonate and dimethyl carbonate as a non-aqueous solvent, and further includes the following general formula (1)
Figure 2011192402
 (However, R represents a methyl group or a hydrogen atom, m represents 0 or 1, and n represents 1 or 2.)
An additive represented by
The non-aqueous electrolyte secondary battery, wherein a charge potential of the positive electrode is 4.4 to 4.6 V based on lithium. 前記非水電解質は、前記添加剤として更にビニレンカーボネートを含んでいることを特徴とする請求項１に記載の非水電解質二次電池。   The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous electrolyte further contains vinylene carbonate as the additive. 前記一般式（１）で表される化合物が、下記化学構造式（２）又は（３）で表される化合物であることを特徴とする請求項１に記載の非水電解質二次電池。
Figure 2011192402
Figure 2011192402
 The non-aqueous electrolyte secondary battery according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following chemical structural formula (2) or (3).
Figure 2011192402
Figure 2011192402
 前記リチウムマンガンニッケル複合酸化物は、ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）で表される化合物であり、
前記正極活物質の全質量を１００質量部としたとき、前記ＬｉＮｉｘＭｎｙＣｏｚＯ２（ｘ＋ｙ＋ｚ＝１）混合量が５〜２５質量部であることを特徴とする請求項１に記載の非水電解質二次電池。 The lithium manganese nickel composite oxide is a compound represented by LiNi x Mn y Co z O 2 (x + y + z = 1),
The amount of the LiNi x Mn y Co z O 2 (x + y + z = 1) mixture is 5 to 25 parts by mass, when the total mass of the positive electrode active material is 100 parts by mass. Non-aqueous electrolyte secondary battery. 前記非水溶媒は、鎖状カーボネートとしてメチルエチルカーボネートを含んでいることを特徴とする請求項１〜４のいずれかに記載の非水電解質二次電池。   The non-aqueous electrolyte secondary battery according to claim 1, wherein the non-aqueous solvent contains methyl ethyl carbonate as a chain carbonate.
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